Preparation of organic compounds



3,965,275 Patented Nov. 20, 1962 3,065,275 PREPARATION OF ORGANIC COMPOUNDS Lloyd Goddard, Detroit, Mich, assignor to Ethyl Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Sept. 1, 1960, Ser. No. 53,369 6 Claims. (Cl. 260--609) This invention relates to a novel and useful process for the preparation of sulfur-containing substituted phenolic compounds. More particularly this invention relates to a process for preparing sulfur-bridged 2,6-dialkyl-pcresols.

The compounds produced by the practice of this invention are extremely useful antioxidants in lubricating oils, rubber and rubber-like materials and a wide range of other organic media.

An object of this invention is to provide a novel chemical process for preparing the above sulfur-containing compounds. A further object is to provide a process which comprises reacting a 3,5-dialkyl-4-hydroxybenzyl chloride with an alkali metal sulfide. Other important objects of this invention will be apparent from the ensuing description. v

The above and other objects of this invention are accomplished by providing a process which comprises reacting a compound having the formula I OH wherein R is an alkyl radical having from 1 to 12 carbon atoms, R is an alpha-branched alkyl radical having from 3 to 12 carbon atoms, R is selected from the group consisting of hydrogen, alkyl radicals having from 1 to 12 carbon atoms and mononuclear aryl radicals having from 6 to 12 carbon atoms, and X is a halogen with an alkali metal sulfide having the formula M 8 wherein M is an alkali metal. The halogen preferred is chlorine but other halogens of an atomic Weight greater than 17 may be used. Chlorine is preferred because of definite cost advantages and its high reactivity. Sodium is preferred as the alkali metal because of its ready availability and high reactivity but, potassium, lithium, rubidium or cesium may also be used.

The preparation of certain preferred reactants of Formula I is disclosed in an application filed concurrently with the present application entitled Organic Aromatic Compounds Serial No. 53,363, the inventor being Joseph D. Odenweller. They can be prepared by reacting a suitable 2,6-dialkylphenol with an aldehyde having from one to 13 carbon atoms and concentrated hydrogen halide. Thus, 2,6-tert-butyl-4-hydroxybenzyl chloride can be prepared by reacting 2,6-ditert-butylphenol with formaldehyde and 35 percent hydrochloric acid.

The benzyl chloride and alkali metal sulfide are preferably present in substantially equimolar quantities. The alkali metal sulfide may also be present in molar excess, up to times the molar concentration of the benzyl chloride. The reaction will proceed when the benzyl chloride is in molar excess, but upon distillation of the product, decomposition of the benzyl chloride makes it undesirable to have it in substantial excess. There is no special order in which the reactants need be mixed. The reaction will proceed equally well when the benzyl chloride is added to the alkali metal sulfide or when the sulfide is added to the chloride.

The solvents used in the practice of this invention may be secondary and tertiary alcohols, ketones, ethers or any suitable polar solvent. For example, the solvents used may be aliphatic secondary or tertiary alcohols having from 3 to 5 carbon atoms such as isopropanol, sec-butyl alcohol and tertiary amyl alcohol; ketones having from three to 13 carbon atoms such as acetone, methylethyl ketone, methyl-n-propyl ketone and benzophenone; the monoethers of the lower glycols such as ethylene glycol monomethyl ether up to ethylene glycol mouoamyl ether; or the cyclic diethers of glycol such as dioxane.

The use of the above solvents facilitates the reaction but it will also proceed when conducted by adding the sulfide directly to the benzyl chloride.

The temperatures employed in practicing this invention vary from about 20 C. to the reflux temperature of the highest boiling solvent, about 305 C., at reaction times of from one-half hour to one week or more to give a good yield of product.

A preferred temperature range is from 80 C. to about 200 C. since the reaction proceeds at a sufliciently rapid rate in this temperature range to give a good yield of product in a reasonable amount of time with a minimum of undesired side reactions.

Although excellent results are obtained throughout the temperature and time ranges stated above, preferred reaction times are from about two hours to about 12 hours. These reaction times give excellent results.

To obtain the elevated temperatures sometimes employed in these reactions, elevated pressure may be used.

However, with most of these compounds, atmospheric pressure is suflicient.

Stirring the reaction mixture facilitates the reaction but is not essential to the process, especially when refluxing the reaction mixture.

The compounds produced by the practice of this invention have the formula II 0 H wherein R R and R are as in Formula I. They are water insoluble, white to yellow crystalline solids. They are ashless, hydrolytically stable and non-volatile, facilitating their incorporation into wide range of organic materials.

The following examples illustrate the practice of this invention according to the method outlined above.

Example I 3 143 C. Infrared absorption analysis shows hindered phenol groups at 2.71 microns, tert-butyl groups at 7.16 and 7.33 microns, and a tetra-substituted benzene ring at 11.32 microns. Analytical: Calculated for C H O S: S, 6.81 percent. Found: S, 6.87 percent.

Example 2 I A solution of 76.3 parts of 3.S-di-tert-butyl-4-hydroxybenzyl chloride (obtained in the manner described in Example 1) in 360 parts isopropanol was stirred at room temperature in the vessel described in Example 1, and 36 parts of Na S.9H O in 40 parts of water was added. Upon addition of the aqueous sodium sulfide there appeared to be a mild heat evolution and some sodium sulfide precipitated from the two-phase mixture. More wa- 'ter (60 parts) was added to dissolve the solids and the two-phase mixture was refluxed for two days. Chilling of the mixture produced purple-colored solids which were filtered ofi, slurried with water (solid turned yellow) and air dried. This material was taken up in isooctane and recrystallized producing oc,oc'-thi0bis (2,6-di-tert-butyl-pcresol) having a melting point of 141 to 142.5 C. Analytical: calculated for C H -O S: Sulfur, 6.81 percent. Found: Sulfur, 6.87 percent.

Example 3 Three hundred and eighty parts of 2-methyl-6-(2'-dodecyl)-4-(a-bromo-n-octynphenol, (prepared by reacting 2-methyl-6-(2'-dodecyl) phenol with 2-ethy1hexanol and hydrobromic acid), is dissolved in 750 parts diacetyl in a reaction vessel equipped with a means for stirring. Fiftyfive parts of Li S in 75 parts of water is added and the mixture is stirred for one week at 20 C. The solvent is stripped and the material is taken up in hot methanol and slowly poured into stirred ice water. The resultant solids are dried and recrystallized from methanol to give a ,a thiobis- [2-methyl-6- 2'-do decyl) -4- 2-ethyl-hexyl) phenol].

Example 4 A solution of 62 parts of 2(3-decyl)-6-(2'-hexyl)- 4-(a-chloro-n-tri-decyl phenol) (prepared by reacting 2-(3-decyl)-6(2-hexyl) phenol with n-tridecaldehyde and hydrogen chloride) in 180 parts of tertiary amyl alcohol is heated together with a solution of 7.8 parts of potassium sulfide in 10 parts of water to 80 C. in a reaction vessel equipped with a stirrer, thermometer and water-cooled condenser, for a period of 12 hours. The mixture is then filtered and recrystallized from isooctane and methanol to give a ,oc '-thiobis-[2-ndecyl-6-(2-hexyl) 4 n tridecylphenol].

Example 5 Thirty-one parts of 2-methyl-6-tert-buty1-4-(a-iodo-nbutyl)phenol (prepared by reacting 2-methyl-6-tert-butyl phenol with n-butyraldehyde and hydriodic acid) in 180 parts of benzophenone (preheated to 60 C.) together with 71 parts of Cs S in parts of water is heated at 305 C. for one half hour in a vessel as described in Example 4 to yield, after filtering and recrystallization, a ,a '-thiobis(2- methyl-6-tert-butyl-4-n-butyl phenol).

Example 6 Using the vessel described in Example 4, 26.9 parts of 2-n-dodecyl-6-tert-butyl 4 (ot-chloro-ethyl) phenol (prepared by reacting 2-n-dodecyl-6-tert-butyl phenol with acetaldehyde and hydrochloric acid) is dissolved in 120 parts of hexarnethylene glycol with heating. To this is added slowly a solution of 8.7 parts of Rb S in parts of water. The mixture is heated to a temperature of 200 C. and is maintained at that temperature with stirring for two hours. It is then cooled, filtered and recrystallized from isooctane and methanol to give a ,ot '-thiobis(2-n-dodecyl- 6-tert-butyl-4-ethyl phenol).

Example 7 A mixture of 9.8 parts of sodium sulfide, 15 parts of water and 119.5 parts of 2,6-diisopropyl-4-( a-chlorop-n-hexylbenzyDphenol (prepared by reacting 2,6-diisopropyl phenol with p-n-hexyl-benzaldehyde and hydrochloric acid) in 250 parts of ethylene glycol n-butyl ether is heated in the vessel described in Example 1, to C. and maintained at that temperature for 12 hours. After cooling, the precipitate is filtered, washed with water, dried and recrystallized from isooctane and methanol to give a ,a '-thiobis-(2,6-diisopropyl-4-p-n-hexylbenzylphenol), a crystalline solid.

Examples of the compounds produced by this invention include: a,a'- thiobis(2-n-butyl-6-tert-butyl-p-cresol) (prepared by the reaction of 3-n-butyl-5-tert-butyl-4-hydroxybenzyl chloride and Na S); a ,ot -thiobis(2-rnethyl-6isopropyl-4-n-butylphenol) (prepared from the reaction of K 8 with a-n-propyl-3-methyl-5-isopropyl-4-hydroxybenzyl chloride); a, x'-thiobis(2-ethyl-6-iSoamyl-p-cresol) (prepared from the reaction of 3-ethyl-5-n-arnyl-4-hydroxybenzyl chloride and Li S) Dt ,d 'fl1lOblS[2-I'lpI'Opy1-6-(3' heptyl)-4-n-heptyl phenol] (prepared from the reaction of C528 and u-n-hexyl-S-n-prOpyl-S-(3-heptyl) 4-hydroxybenzyl chloride); a,u'-thiobis(2,6-diisopropyl p cresol) (prepared from the reaction of 3,5-diisopropyl-4-hydroxybenzyl chloride and Rb S); m ,a '-thiobis[2-n-butyl-6-(2- nonyl)-4-n-dodecyl phenol] (prepared from the reaction of Na s with a n-undecyl-3-n-butyl-5-(2 nonyl) 4 hydroxybenzyl chloride); a,ot'-thiobis(2,6 di tert butyl-pcresol) (prepared from the reaction of 3,5-di-tert-butyl- 4-hydroxybenzyl chloride and Na S); ot ,et -thiobis[2-namyl-6-(4'-dodecyl)-4-n-butyl phenol] (prepared from the reaction of Na S and tx-n-propyl-3-n-arnyl-5-(4'-dodecyl)- 4-hydroxybenzyl chloride); a,u'-thiobis(Z-n-heptyl-G-tertbutyl-p-cresol) (prepared from the reaction of 3-n-heptyl- 5-tert-butyl-4-hydroxybenzyl chloride and Na s); 00 ,06 thiobis(2-n-nonyl-6-isopropyl-4-ethyl phenol) (prepared from the reaction of a-methyl-B-n-nonyl-5-isopropyl-4- hydroxybenzyl chloride and Na S; a,oc'-thiObiS(2n-d0- decyl-6-sec-butyl-p-creso1) (prepared from the reaction of 3-n-dodecyl-5 sec butyl 4 hydroxybenzyl chloride and Na S); u ,ot '-thiobis(3,6-di-tert butyl 4 benzylphenol) (prepared from the reaction of Na S with a-phenyl-3,5-ditert butyl 4 hydroxy benzyl chloride); 11,06 thiobis [2- methyl-6-tert-butyl 4(4-hexylphenyl)phenol] (prepared from the reaction of Na s and a(4'-hexylphenyl) 3-rnetl1yl- 5-tert-butyl-4-hydroxybenzyl chloride).

In a preferred embodiment of this invention, the compounds to be produced are compounds of Formula 11 wherein R is hydrogen. These compounds are preferred because of their ease of preparation from readily available starting materials and greater antioxidant activity. Among the compounds prepared by this preferred embodiment are: a,a'-thiobis[2-isopropyl-6-(3-nonyl)-p-cresol] (prepared from the reaction of Na S and 3-isopropyl-5-(3'- nonyl) 4 hydroxybenzyl chloride); 0:,0c' thiobisEZ npropyl-6-(2-octyl)-p-cresol] (prepared from the reaction of Na S and 3-n-pr0pyl-5 (2 octyl) 4 hydroxybenzyl chloride); u,Oc'-lhlOblS[2-SC butyl 5 (3' doclecyl)-pcresol] (prepared from the reaction of Na S with 3-secbutyl-5-( 3 -dodecyl -4-hydroxybenzyl-chloride) ot,ot'-'[hi0- bis(3-methyl-6-isopropyl-p-cresol) (prepared from the reaction of 3-methyl-5-isopropyl-4-hydroxybenzyl chloride and Na S); a, w.'-thiobis[2-ethyl-6-(2-dodecyl)-pcresol] (prepared from the reaction of 3-ethyl-5-(2-dodecyl)-4-hydroxybenzyl chloride and Na s); a,et-thiobis (3-methyl-6-isopropyl-p-cresol) (prepared from the reaction of Na s and 3-methyl-5-isopropyl-4-hydroxy benzyl chloride); a,a'-thiobis(2-methyl-6 tert butyl p cresol) (prepared from the reaction of Na S and 3-methyl-6-tertbutyl-4-hydroxybenzyl chloride).

The most particularly preferred compound produced by the practice of this invention is u,a-thiobis(2,6-di-tertbutyl-p-cresol) (prepared from the reaction of Na s and 3,5-di-tert-butyl-4-hydroxy-benzyl chloride) which is a most superior antioxidant in lubricating oils and other emai organic media and is most readily and economically prepared.

The compounds produced by the practice of this invention are outstanding antioxidants. Therefore, a specific utility of this invention in a new composition of matter which comprises organic material normally tending to undergo oxidative deterioration in the presence of air, oxygen or ozone containing an appropriate quantityfrom 0.001 up to about 5 percent, and preferably from about 0.25 to about 2 percent-of a compound produced by this invention.

The compounds produced by this invention find important utility as antioxidants in a wide variety of oxygensensitive material. Thus, liquid hydrocarbon fuels such as gasoline, kerosene and fuel oil are found to possess increased storage stability by the use of an antioxidant produced by this invention. Likewise, liquid hydrocarbon fuels such as gasoline which contain organometallic additives such as tetraethyllead as well as other organome-tallic compounds which. are used as fuel additives attain appreciably increased oxidative stability by the use of compounds produced by the practice of this invention. In addition, lubricant oils and functional fiuids, both those derived from naturally occurring hydrocarbons and those synthetically prepared are greatly enhanced by compounds produced by the practice of this invention. The addition of small quantities of the compounds produced by this invention to such materials as turbine, hydraulic, transformer and other highly refined industrial oils, soaps and greases; plastics; synthetic polymers such as polyethylene and polypropylene; orgauometallic compositions where such fluids contain tetraethyllead and tetraethyllead antiknock mixtures as well as other organometallics; elastomers, including natural rubber; lubricating greases; crankcase lubricating oil; and the like, greatly increase resistance to deterioration in the presence of air, oxygen or ozone.

The compounds produced by this invention are also very useful in protecting petroleum waxparaffin wax and microcrystalline wax-against oxidative deterioration. They also find use in the stabilization of edible fats and oils of animal and vegetable origin which tend to become rancid, especially during long periods of storage because of oxidative deterioration. Typical representatives of these edible fats and oils are linseed oil, cod liver oil, castor oil, soy bean oil, rape seed oil, coconut oil, olive oil, palm oil, corn oil, sesame oil, peanut oil, babassu oil, butter fat, lard, beef tallow, and the like.

The compounds produced by the practice of this invention are also useful in preventing oxidative deterioration in lubricating oil compositions. Thus, a specific utility of thi invention is a lubricating oil normally susceptible to oxidative deterioration in small antioxidant quantity up to 5 percent of a compound as defined above.

To prepare such superior lubricants of this invention an appropriate quantity-from about 0.01 to about 5 percent and preferably from about 0.25 to about 2 percent of compound produced by thi invention is blended with the base oil to be protected. Suitable base oils include mineral oils and also synthetic diester oils such as sebacates, adipates, etc., which find particular use as aircraft instrument oils, hydraulic and damping fluids and precision bearing lubricants. All of these base oils are normally susceptible to oxidative deterioration, especially at elevated temperatures. The finished lubricants of this invention have much greater oxidation stability and many other improved performance characteristics as compared with the corresponding base oils.

To illustrate the benefits obtained by the practice of this invention a standard oil oxidation test is used. The equipment and test procedure described by Kroger et al., Erdol and Kohle, 2, page 398 (1949), served as a basis for the tests. The equipment and procedures are slightly modified in order to make the oxidizing conditions more strenuous.

In this manner the test lubricants are subjected to severe oxidizing conditions in order to conclusively establish the effectiveness of additives under very adverse conditions. Furthermore, the modifications are found to provide re sults which correlated extremely well with test result of other standard procedures, including actual engine tests.

The equipment consists of a reaction cell connected with an open end monometer whereby the total uptake of oxygen by the oil is determined by noting the drop in height of the mercury in the monorneter. The test oil sample is placed in the reaction cell which is then flushed with Oxygen and the temperature is then raised and held at that selected for the test until the substrate oil undergoes catastrophic oxidation which is shown by a rapid oxygen uptake. In all cases the test oil is deliberately contaminated with iron hexoate as an oxidation promoter. In tests of this nature, the oxidation stability of a test lubricant is determined by measuring its induction period, that is, the time required for catastrophic deterioration under the above outlined conditions. The longer the induction period, the more stable the lubricant. In tests of this nature, at 150 C., a base oil containing no additive had an induction time of three minutes while the same oil containing l.0 l0 moles/liter of u,a'-thiobis(2,6-di-tert-butyl-p-cresol) had an induction time of 129 minutes, thus increasing the induction time by a factor of 43.

To further show the useful propertie of the novel compounds of this invention, recourse is had to the Polyveriform Oxidation Stability Test as described in the paper entitled Factors Causing Lubricating Oil Deterioration in Engines find. and Eng. Chem, Anal. Ed, 17, 302 (1945 1. See also A Bearing Corrosion Test for Lubricating Oils and Its Correlation with Engine Performance, [Al. Chem, 21, 737 (1949)]. This test effectively evaluates the performance of lubricating oil antioxidants. The test equipment procedure employed and correlations of the results with engine performance are discussed in the first paper cited above. By employing various compounds produced by the practice of this invention in oxygen-sensitive lubricating oil, effective inhibition of oxidative deterioration is achieved.

Comparative tests were conducted using the method and apparatus essentially as described in the publication above entitled Factors Causing Lubricating Oil Deterioration in Engines. One minor modification was that the steel sleeve and copper test piece described in this publication were omitted from the apparatus. In these tests an initially additive-free V1. solvent-refined SAE-lO crankcase oil was used. The principal test conditions consisted of passing 70 liters of air per hour through the test oil for a total period of 20 hours while maintaining the oil at a temperature of 300 F. Oxidative deterioration of the oil was further promoted by employing as oxidation catalysts 0.05 percent by weight of ferric oxide (as ferric 2- ethyl hexoate) and 0.10 percent by Weight of lead bro mide, both of these amounts being based upon the weight of oil employed.

Lubricating oils were prepared by blending one percent by weight of a,m-thiobis(2,6-di-tert-butyl-p-cres0l) with the oil described above. These compositions were compared in the Polyveriform Test with a sample of the oil not containing the antioxidant. Whereas during the test the oil containing no antioxidant increases in acid number to a high acid number and shows a tremendous increase in viscosity, the samples containing the antioxidants of this invention show only a slight acid number and an unappreciable increase in viscosity, thus showing an unusual improvement over the base oil.

Although compounds of this invention have been illustrated by compounds in which the two phenolic radicals are identical, compounds in which the two phenolic radicals are different can also be prepared and are embraced within the invention. Thus, a mixture of benzyl halides can be reacted with an alkali metal sulfide to form a mixture of thio ethers. Depending on the reactants and reaction conditions there is a distribution of diphenolic thio ethers products. Thus, in an embodiment of this invention 100 parts of 2,6-di-tert-butyl-4-hydroxybenzyl chloride, 87 parts of 2,6-diisopropyl-4-hydroxybenzyl chloride and 39 parts of Na S can be reacted to produce a mixture of about 25 percent a,a-thiobis(2,6-diisopropyl-p-cresol), about 25 percent u,a-thiobis(2,G-di-tert-butyl-p-cresol) and about 50 percent (3,5-diisopropyl-4-hydroxybenzyl)- (3,5di-tert butyl-4-hydroxybenzyl) thio ether. The mix ture itself finds utility as an antioxidant. Indeed, in many applications the mixture is preferred over the individual components because of solubility, melting point and boiling point considerations. The mixture can also be distilled to separate the component compounds, each component showing antioxidant activity.

A further example of the reaction of mixing benzyl halides with an alkali metal sulfide is the reaction of 3-methyl-5-tert-butyl-4-hydroxybenzyl bromide with 3(2'- dodecyl)-5-(3'-dodecyl) 4 hydroxylbenzyl bromide and U 5 to produce a mixture of a,a-thiobis(2-methyl-6-tertbutyl-p-cresol), ot,o1,'-'thlObiS[2 (2-dodecyl)-6-(3'-dodecy1)-p-cresol] and [3-rnethyl 5 tert-butyl-4-hydroxybenzyl]-[3-(2-dodecyl)-5-(3-dodecyl) 4 hydroxybenzyl] thioether. Likewise, 2,6-di-sec-butyl-4-(a-iodo-n-octyl) phenol can be reacted with 2(3'-octyl)-6-(2-heptyl)-4- (oc-chloro-p-n-hexylbenzyl)phenol and K S to form a mixture of [3,S-di-sec-butyl-a-n-heptyl-4-hydroxybenzyl]-[3- (3'-octyl)-5-(2'-heptyl)-u-p-n-hexylphenyl 4 hyd'roxybenzyl] thioether, u ,a 'thiobis l 2-(3'-octy1) 6 (2'-heptyl)-4-p-n-hexylbenzy1 phenol] and a ,ot '-thiobis(2,6-disec-butyl-4-n-octylphenol). Also, 3 ethyl-5-isopropyl-4- hydroxybeuzyl chloride can be reacted with 2-n-propyl6 sec-butyl-4-(ot-bromo-n-amyDphenol and C828 to yield a,u'-trithio-bis(Z-ethyl-6-isopropyl-p-cresol), a ,a trithiobis(2-n-propyl-6-sec-butyl-4-n-amylphenol) and (3-ethyl-5-isopropyl-4-hydroxybenzyl)-(3-n-propyl 5 sec-butyl-a-n-butyl-4-hydroxybenzyl) thioether. Further, 2-11- butyl-6-(3' nonyl)-4-(u-chloro-n-tridecyl) phenol can be reacted with 2-n-decyl-6-(4-decyl)-4-(a-chloro ethyl) phenol and Rb S to give a mixture of [3-n-butyl-5-(3'- nonyl)-a-n-dodecyl 4 hydroxybenzyl]-[3-n-decyl-5-(4- decyl)-01-methyl-4-hydroxybenzyl] thioether, a ,a -thiobis [2-n-butyl-6-(3-nonyl)-4--n-tridecylphenol] and a ,ot -thiobis [2-n-decyl-6- 4-decyl) -4-ethylphenol] I claim:

1. A process for preparing a compound having the formula wherein R is an alkyl radical having from one to 12 carbon atoms, R is an alpha-branched alkyl radical having from 3 to 12 carbon atoms and R is selected from the group consisting of hydrogen, alkyl radicals having from one to 12 carbon atoms and mononuclear aryl radicals having from 6 to 12 carbon atoms, which comprises reacting a compound having the formula wherein R is an alkyl radical having from one to 12 carbon atoms, R is an alpha-branched alkyl radical having from 3 to 12 carbon atoms, R is selected from the group consisting of hydrogen, alkyl radicals having from one to 12 carbon atoms, and mononuclear aryl radicals having from 6 to 12 carbon atoms, and X is a halogen, with an alkali metal sulfide having the formula, M 3, wherein M is an alkali metal, in a solvent selected from the group consisting of secondary alcohols, tertiary alcohols, ketones and ethers.

2. The process of claim 1 wherein R is hydrogen, X is chlorine and M is sodium.

3. The process for preparing a,u-thiobis(2,6-di-tertbutyl-p-cresol) which comprises reacting 3,5-di-tert-butyl- 4-hydroxybenzyl chloride with Na S, in a solvent selected from the group consisting of secondary alcohols, tertiary alcohols, ketones and ethers.

4. The process of claim 3 wherein said solvent is iso propanol.

5. The process for preparing a,a'-thiobis(2-methyl-6- tert-butyl-p-cresol) which comprises reacting 3-methyl-5- tert-butyl-4-hydroxybenzyl chloride with Na s, in a solvent selected from the group consisting of secondary alcohols, tertiary alcohols, ketones and ethers.

6. The process of claim 5 wherein said solvent is isopropanol.

References Cited in the file of this patent UNITED STATES PATENTS 2,488,134 Mikeska et a1 Nov. 15, 1949 

1. A PROCESS FOR PREPARING A COMPOUND HAVING THE FORMULA 